稠油硫酸盐热化学还原生成HS实验研究

An Experimental Investigation of HS Production by Thermochemical Sulfate Reduction in Heavy Oil

马强 林日亿 韩超杰 袁高亮 于万民

MAQiang LINRiyi HANChaojie YUANGaoliang YUWanmin

中国石油大学(华东)储运与建筑工程学院, 山东 青岛 266580 潍坊市市政工程设计研究院有限公司, 山东 潍坊 261061 临沂市阳光热力有限公司, 山东 临沂 273411

College of Pipeline and Civil Engineering, China University of Petroleum(East China), Qingdao, Shandong 266580, China Weifang Municipal Engineering Design Research Institute Co. Ltd., Weifang, Shandong 261061, China Linyi Yangguang Heating Power Ltd., Linyi, Shandong 273411, China

为了研究稠油注汽热采过程中生成HS机理，以NaSO，CaSO，MgSO，Fe（SO），Al（SO）与稠油硫酸盐热化学还原（TSR）实验为基础，探究稠油TSR生成HS机理。实验表明，不同硫酸盐与稠油反应生成HS不尽相同，硫酸盐的阳离子所带电荷数决定TSR反应程度的难易，电荷数越多越容易进行反应，且HS生成量顺序为Al（SO）>Fe（SO） > MgSO > CaSO > NaSO，但生成的烃量顺序为Fe（SO） > Al（SO） > MgSO > CaSO > NaSO。与其他硫酸盐不同的是，由于Fe（SO）的氧化性，Fe可能与生成的HS进一步反应。通过傅里叶红外变换光谱（FT-IR）对固相检测发现，不仅存在金属氧化物（CaO，MgO，FeO，AlO）还存在FeS。最后，通过对MgSO油相硫含量的检测发现，反应后硫含量高于原油硫含量，证明了无机硫向有机硫的转化。

The mechanism of HS formation during heavy oil recovery by steam injection was investigated by reacting five sulfates (NaSO, CaSO, MgSO, Fe(SO), and Al(SO)) with heavy oil via thermochemical sulfate reduction(TSR). Significant variations were observed in the production of HS depending on the type of sulfate reacting with the heavy oil, as the number of charges carried by the sulfate cation governed the ease of the TSR reaction. More strongly charged sulfate cations facilitated the TSR reaction. The HS yields of the sulfates followed the order:Al(SO) > Fe(SO) > MgSO > CaSO > NaSO. However, the hydrocarbon yields were as follows:Fe(SO) > Al(SO) > MgSO > CaSO > NaSO. Fe(SO) is unique among the sulfates as it can react with HS due to its oxidizing property. The solid-state Fourier transform infrared spectroscopy (FTIR) analyses showed that FeS was present in addition to several metal oxides (CaO, MgO, FeO, and AlO). Finally, the sulfur content of the oil phase with the TSR reaction of MgSO was analyzed, and it was demonstrated that the post-TSR sulfur content of the oil phase was higher than that of crude oil. This confirmed that inorganic sulfur was converted to organic sulfur during the TSR reaction in heavy oil.

10.11885/j.issn.1674-5086.2018.06.01.01